EP1292593A2 - 2-(3,5-disubstituierte-4-pyridyl)-4-(thienyl, thiazolyl oder arylphenyl)-1,3-oxazolinverbindungen - Google Patents
2-(3,5-disubstituierte-4-pyridyl)-4-(thienyl, thiazolyl oder arylphenyl)-1,3-oxazolinverbindungenInfo
- Publication number
- EP1292593A2 EP1292593A2 EP01950425A EP01950425A EP1292593A2 EP 1292593 A2 EP1292593 A2 EP 1292593A2 EP 01950425 A EP01950425 A EP 01950425A EP 01950425 A EP01950425 A EP 01950425A EP 1292593 A2 EP1292593 A2 EP 1292593A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- compound
- alkyl
- haloalkyl
- mmol
- nmr
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
- A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
Definitions
- This invention provides new 2-(4-pyridyl)-oxazoline compounds that are useful as insecticides and acaricides. More particularly, the present invention concerns 2-(3,5-disubstituted-4-pyridyl)-l,3-oxazoline compounds and certain of their stereoisomers. The invention also includes new synthetic procedures and intermediates for preparing the compounds, pesticide compositions containing the compounds, and methods of controlling insects and mites using the compounds.
- Certain 3-(3,5-disubstituted-4-pyridyl)-lH-l,2,4-triazoles with activity against mites and insects are disclosed in WO 00/24735.
- 2-(Substituted-phenyl)- 1,3-oxazolines with insecticidal activity are disclosed in JP 4-89484, EP 0345775- Al, EP 0432661-A2, EP 0553623-A1, WO 99/01443, WO 99/23081 and WO 98/47881.
- 2-Aryl- and 2-heteroaryl-l,3-oxazolines with acaricidal and insecticidal activity are disclosed in JP 6-145169 and WO 99/65901.
- This invention provides novel substituted pyridyl oxazoline derivatives especially useful for the control of insects and mites.
- the invention provides novel insecticidally active compounds of the formula (I)
- R represents H, (Ci-Cg) alkyl, (Ci-Cg) haloalkyl, -C ⁇ ) alkenyl, (C2- C ) alkynyl, or (C1-C6) alkoxyalkyl;
- R 2 represents H, halogen, (C1-C6) alkyl, (Ci-Cg) haloalkyl, (Ci-C ⁇ ) alkoxy, (Ci-Cg) haloalkoxy;
- Q is a group selected from
- R 3 represents H, halogen, (Cj-Cg) alkyl, (C7-C21) straight chain alkyl, hydroxy, (Ci -C6) alkoxy, (Ci -Cg) haloalkyl, (Ci-Cg) haloalkoxy, (Ci-Cg) alkoxyalkyl, (Ci -Cg) alkoxyalkoxy, (C2-Cg) alkenyl, (C2-Cg) haloalkenyl, CN,
- R represents H, halogen, (C1-C6) alkyl, (Ci-Cg) alkoxy, (Ci-Cg) haloalkyl, (C!-C 6 ) haloalkoxy, CN, CO 2 , CON(R ) 2 , (C ⁇ -C 6 ) S(O) m alkyl or (C!-C 6 )S(O) m haloalkyl; s
- R represents
- R is H, (Ci-Cg) alkyl, (Ci-Cg) haloalkyl, (C 2 -C 6 ) alkenyl, (C 2 -C 6 ) alkynyl, phenyl, or substituted phenyl;
- R 7 and R 8 are independently CI, F, methyl, halomethyl, methoxy, or halomethoxy;
- n O, l, or 2;
- n 1 or 2;
- Preferred compounds of formula (I) include the following classes:
- R 4 and R 5 are as defined in formula (I).
- R 3 and R 4 are as defined in formula (I).
- the invention also provides new processes and intermediates for preparing compounds of formula (I) as well as new compositions and methods of use, which will be described in detail hereinafter.
- alkyl alkenyl and alkynyl
- derivative terms such as “alkoxy” and “alkanoyl”, as used herein, include within their scope straight chain, branched chain and cyclic moieties.
- alkenyl and alkynyl are intended to include one or more unsaturated bonds.
- halogen refers to fluorine, chlorine, bromine, and iodine. Preferred halogens are fluorine and chlorine.
- halomethyl refers to methyl, alkyl, and alkenyl groups substituted with from one up to the maximum possible number of halogen atoms.
- halomethoxy refers to methoxy and alkoxy groups substituted with from one up to the maximum possible number of halogen atoms .
- substituted pyridyl refers to the ring system substituted with one or more groups independently selected from halogen, (C1-C4) alkyl, (C1-C4) haloalkyl, CN, O2, phenyl, (Ci -C4) alkoxy, or (C1-C4) haloalkoxy.
- substituted phenyl refers to a phenyl group substituted with one or more groups independently selected from halogen
- C ⁇ ) haloalkyl (Ci -C7) hydroxy alkyl, (Ci -C7) alkoxy, (C1-C7) haloalkoxy, phenoxy, phenyl, NO2, OH, CN, (C1-C4) alkanoyl, benzoyl, (C1-C4) alkanoyloxy, (C1-C4) alkoxy carbonyl, phenoxy carbonyl, or benzoyloxy.
- the compounds of this invention can exist as one or more stereoisomers.
- the various stereoisomers include geometric isomers, diastereomers and enantiomers.
- the compounds of the present invention include racemic mixtures, individual stereoisomers and optically active mixtures. It will be appreciated by those skilled in the art that one stereoisomer may be more active than the others. Individual stereoisomers and optically active mixtures may be obtained by selective synthetic procedures, by conventional synthetic procedures using resolved starting materials or by conventional resolution procedures.
- step a of Scheme A the compound of formula (A) can be reacted with an aminoacid ester (J. Org. Chem. 1991, 56, 420) to afford a compound of formula (B).
- an aminoacid ester J. Org. Chem. 1991, 56, 420
- 1,2-Dichloroethane is the preferred solvent, however other polar aprotic solvents such as pyridine or THF can also be used.
- step b of Scheme A the compound of formula (B) can be reacted with a reducing agent such as sodium borohydride to afford a compound of formula (C) in an organic solvent such as ethanol, at a temperature in the range from 0 °C to ambient temperature.
- a reducing agent such as sodium borohydride
- step c of Scheme A the compound of formula (A) can be reacted with an aminoalcohol (D) to afford a compound of formula (C).
- 1,2-Dichloroethane is the preferred solvent, however other polar aprotic solvents such as pyridine or THF can also be used.
- step d of Scheme A the N-amidealcohol of formula (C) can be reacted with either (diethylamino)sulfur trifluoride (DAST) to provide the product of formula (I) or with thionyl chloride.
- DAST diethylamino)sulfur trifluoride
- the ring closure reaction is carried out in dichloromethane, 1,2-dichloroethane or neat at a temperature in the range from -78 °C to ambient temperature.
- step a of Scheme B the oxazoline of formula (la) is reacted under standard Suzuki coupling reaction conditions with an appropriately substituted R - boronic acid to provide the product of formula (lb).
- the coupling reaction is carried out in an acetonitrile/water mixture, or ethanol, at a temperature in the range from ambient to refluxing temperature.
- Catalytic amounts of dichlorobis(triphenylphosphine)palladium(II) or tetrakis(triphenylphosphine)- palladium(O) are typically used for coupling, however other Pd(II) or Pd(0) catalysts can also be used.
- sodium carbonate is used as base in the coupling reaction but other inorganic or organic bases such as potassium carbonate or triethylamine can also be used.
- R 1 , Q, R 7 and R 8 are as defined in formula (I) provided that R 1 does not represent H.
- step a of Scheme C the compound of formula (A) is reacted with an aminoalcohol (D) to afford a compound of formula (C).
- 1,2-Dichloroethane is the preferred solvent, however other polar aprotic solvents such as pyridine or THF can also be used.
- the ring closure step b of Scheme C is similar to step d of Scheme A and provides the products of formula Syn (I) and Anti (I) which can be separated by using chromatographic techniques.
- Q represents
- R 1 , Q, R 4 , R 5 , R 7 and R 8 are as defined in formula (I) provided-that R 1 does not represent H.
- the Suzuki coupling step a of Scheme D is similar to step a of Scheme B and provides products of formula Syn (lb) and Anti (lb) which can be separated by using chromatographic techniques.
- step a of Scheme E the compound of formula (E) is reacted with a mixture of potassium acetate and tetrabutylammonium chloride at refluxing temperature of dichloroethane to afford a compound of formula (F).
- Dichloroethane is the preferred solvent, however other chlorinated solvents such as dichloromethane or carbon tetrachloride can be used.
- the transformation can also be carried out using inorganic acetates such as sodium acetate with other phase transfer catalysts such as tetrabutylammonium bromide or iodide.
- step b of Scheme E the compound of formula (F) is reacted with potassium acetate in ethanol followed by treatment with methoxylamine hydrochloride to provide the compound of formula (G).
- step c of Scheme E the compound of formula (G) is reacted with a reducing agent such as sodium borohydride in trifluoroacetic acid to provide the compound of formula (D) in an organic solvent such as tetrahydrofuran.
- a reducing agent such as sodium borohydride in trifluoroacetic acid
- reaction can be performed at ambient to refluxing temperature.
- product can be isolated as a salt, preferably as the HC1 salt.
- the reaction mixture was heated to 70 °C for 3 hours and then cooled to 25 °C.
- the pH was adjusted to ⁇ 3 by the careful addition of cone. HCl to neutralize the remaining NaBH 4 .
- the pH was adjusted to >9 with 50% aq. NaOH.
- Water (100 mL) and dichloromethane (200 mL) were added and the phases were separated.
- the aqueous phase was extracted with dichloromethane (3 X 100 mL).
- the combined organic phases were washed with brine, dried over sodium sulfate, filtered, and the solvents were removed under reduced pressure to give crude product.
- the product was purified by suspending in dichloromethane and bubbling anhydrous HCl gas to produce the HCl salt.
- the salt was filtered and dried to give product as a white solid (6.5 g, 72% yield): mp 200-206 °C.
- N-(4-Bromophenylglycine methyl ester)-3 ,5-dichloro-4-pyridinyl carboxamide (13.5 mmol, 5.65 g), sodium borohydride (54.0 mmol, 2.04 g), and calcium chloride (27.0 mmol, 3.0 g) were combined in THF (20 mL) and ethanol (40 mL) and stirred at ambient temperature for 36 hours.
- the yellow suspension was poured into 1 M Sodium Acetate (100 ml) and stirred 20-30 min. before extracting with EtOAc.
- the organic extract was washed with brine and dried over MgSO 4 . Filtration and concentration in vacuo afforded a yellow solid (5.24 g). Chromatography (SiO 2 , EtOAc) afforded the product as a white solid. (2.44 g, 57.5% yield): mp 152-155 °C.
- Example 5 For C 14 H 9 F 2 N 2 O; Calculated: C,
- Lithium-3,5-dichloropyridine-4-carboxylate (0.54 g, 2.7 mmol) was suspended in 1,2-dichloroethane (10 mL).
- Thionyl chloride (0.42 mL, 5.7 mmol) and dimethylformamide (3 drops from a Pasteur pipette) were added. After refluxing under nitrogen for 5.5 hours, the reaction mixture was cooled to room temperature and concentrated under reduced pressure. 1,2-Dichloroethane (20 mL) was added to the residue and re-concentrated under reduced pressure.
- the brown residue was taken up in dry tetrahydrofuran (2.5 mL) and added to a suspension of l-amino-2-hydroxy-l-(4-iodophenyl)propane hydrochloride (0.85 g, 2.7 mmol) in dry tetrahydrofuran (5 mL) at -5 °C. The addition rate was controlled to keep reaction temperature at 0 °C. The reaction mixture was stirred at room temperature for 14 hours. Methylene chloride (20 mL) and water (20 mL) were added to the reaction mixture and the organic layer was collected. The aqueous layer was extracted with more methylene chloride (2 X 10 mL).
- N-[2-Hydroxy-l-(4-iodophenyl)-propyl]-2,5- dichloroisonicotinamide (918 mg, 2 mmol) was dissolved in methylene chloride (220 mL) and cooled to -78 °C. To this cloudy suspension was added (diethylamino)sulphur trifluoride (0.33 g, 2 mmol) at a dropwise rate over 10 minutes. The reaction mixture was allowed to come to room temperature overnight and poured into crushed ice (80 g) containing ammonia solution (10 mL). The organic layer was collected and the aqueous layer was extracted with methylene chloride (2 X 50 mL).
- (I) are also within the scope of the invention.
- boron tetrafluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide, hydrogen sulfate, or organic acid salts may be used.
- the compounds identified in the following Tables were prepared using the procedures illustrated in the foregoing examples, and the compounds were tested against tobacco budworm (TBW), beet armyworm (BAW), cabbage looper (CL), cotton aphid (CA), two-spotted spider mite (SM), and sweetpotato whitefly (WF) using procedures described hereinafter.
- TW tobacco budworm
- BAW beet armyworm
- CL cabbage looper
- CA cotton aphid
- SM two-spotted spider mite
- WF sweetpotato whitefly
- TBW refers to activity at 400 ppm against tobacco budworm
- BAW refers to activity at 400 ppm against beet armyworm
- CL refers to activity at 400 ppm against cabbage looper
- CA refers to activity at 50 ppm against cotton aphid
- SM refers to activity at 2.5 ppm against two-spotted spider mite
- WF refers to activity at 200 ppm against whitefly
- the compounds of the invention are useful for the control of insects, mites, and aphids. Therefore, the present invention also is directed to a method for inhibiting an insect, mite, or aphid which comprises applying to a locus of the insect or mite an insect- or mite-inhibiting amount of a compound of formula (I).
- the compounds are useful for reducing populations of insects and mites and are useful in a method of inhibiting an insect or mite population which comprises applying to a locus of the insect or mite an effective insect- or mite- inactivating amount of a compound of formula (I).
- locus of insects or mites is a term used herein to refer to the environment in which the insects or mites live or where their eggs are present, including the air surrounding them, the food they eat, or objects which they contact.
- plant-ingesting insects or mites can be controlled by applying the active compound to plant parts that the insects or mites eat, particularly the foliage.
- the compounds might also be useful to protect textiles, paper, stored grain, or seeds by applying an active compound to such substance.
- inhibiting an insect or mite refers to a decrease in the numbers of living insects or mites, or a decrease in the number of viable insect or mite eggs. The extent of reduction accomplished by a compound depends, of course, upon the application rate of the compound, the particular compound used, and the target insect or mite species. At least an inactivating amount should be used.
- the terms “insect-inactivating amount” and “mite-inactivating amount” are used to describe the amount, which is sufficient to cause a measurable reduction in the treated insect or mite, population.
- the present invention is directed to a method for inhibiting a mite or aphid which comprises applying to a plant an effective mite- or aphid- inactivating amount of a compound of formula (I).
- Insecticidal test for tobacco budworm Heliothis virescens). beet armyworm (Spodoptera exisua . and cabbage looper (Trichoplusia ni).
- each dried, treated cotton cotyledon disc was infested with a 2 nd instar tobacco budworm larva, and each cabbage leaf disc was infested with a 2 nd instar cabbage looper larva.
- Cups containing the treated substrates and larvae were capped and then held in a growth chamber at 25 °C, 50-55% RH, and 14 hr light: 10 hr dark for 5 days. The number of dead insects of 5 per species per treatment was then determined and the results are given in Tables 1-4.
- each test compound was dissolved by adding 4 mL of a 90: 10 acetone: ethanol solvent mixture to the vial containing the sample compound.
- Another aspect of the invention is a method of protecting a plant from insects which comprises treating plant seed prior to planting it, treating soil where plant seed is to be planted, or treating soil at the roots of a plant after it is planted, with an effective amount of a compound of formula (I).
- compositions which are important embodiments of the invention, and which comprise a compound of this invention and a phytologically-acceptable inert carrier.
- the compositions are either concentrated formulations that are dispersed in water for application, or are dust or granular formulations that are applied without further treatment.
- the compositions are prepared according to procedures and formulae which are conventional in the agricultural chemical art, but which are novel and important because of the presence therein of the compounds of this invention. Some description of the formulation of the compositions will be given, however, to assure that agricultural chemists can readily prepare any desired composition.
- the dispersions in which the compounds are applied are most often aqueous suspensions or emulsions prepared from concentrated formulations of the compounds.
- Such water-soluble, water-suspendable or emulsifiable formulations are either solids, usually known as wettable powders, or liquids usually known as emulsifiable concentrates or aqueous suspensions.
- Wettable powders which may be compacted to form water dispersible granules, comprise an intimate mixture of the active compound, an inert carrier, and surfactants.
- the concentration of the active compound is usually from about 10% to about 90% by weight.
- the inert carrier is usually chosen from among the attapulgite clays, the montmorillonite clays, the diatomaceous earths, or the purified silicates.
- Effective surfactants comprising from about 0.5% to about 10% of the wettable powder, are found among the sulfonated lignins, the condensed naphthalenesulfonates, the naphthalenesulfonates, the alkylbenzenesulfonates, the alkyl sulfates, and nonionic surfactants such as ethylene oxide adducts of alkyl phenols.
- Emulsifiable concentrates of the compounds comprise a convenient concentration of a compound, such as from about 50 to about 500 grams per liter of liquid, equivalent to about 10% to about 50%, dissolved in an inert carrier which is either a water miscible solvent or a mixture of water-immiscible organic solvent and emulslfiers.
- a compound such as from about 50 to about 500 grams per liter of liquid, equivalent to about 10% to about 50%, dissolved in an inert carrier which is either a water miscible solvent or a mixture of water-immiscible organic solvent and emulslfiers.
- Useful organic solvents include aromatics, especially the xylenes, and the petroleum fractions, especially the high-boiling naphthalenic and olefinic portions of petroleum such as heavy aromatic naphtha.
- Suitable emulsifiers for emulsifiable concentrates are chosen from conventional nonionic surfactants, such as those discussed above.
- Aqueous suspensions comprise suspensions of water-insoluble compounds of this invention, dispersed in an aqueous vehicle at a concentration in the range from about 5% to about 50% by weight. Suspensions are prepared by finely grinding the compound, and vigorously mixing it into a vehicle comprised of water and surfactants chosen from the same types discussed above.
- Inert ingredients such as inorganic salts and synthetic or natural gums, may also be added, to increase the density and viscosity of the aqueous vehicle. It is often most effective to grind and mix the compound at the same time by preparing the aqueous mixture, and homogenizing it in an implement such as a sand mill, ball mill, or piston-type homogenizer.
- the compounds may also be applied as granular compositions, which are particularly useful for applications to the soil.
- Granular compositions usually contain from about 0.5% to about 10% by weight of the compound, dispersed in an inert carrier which consists entirely or in large part of clay or a similar inexpensive substance.
- Such compositions are usually prepared by dissolving the compound in a suitable solvent and applying it to a granular carrier which has been pre-formed to the appropriate particle size, in the range of from about 0.5 to 3 mm.
- Such compositions may also be formulated by making a dough or paste of the carrier and compound and crushing and drying to obtain the desired granular particle size.
- Dusts containing the compounds are prepared simply by intimately mixing the compoxmd in powdered form with a suitable dusty agricultural carrier, such as kaolin clay, ground volcanic rock, and the like. Dusts can suitably contain from about 1% to about 10% of the compound.
- Insecticides and acaricides are generally applied in the form of a dispersion of the active ingredient in a liquid carrier. It is conventional to refer to application rates in terms of the concentration of active ingredient in the carrier. The most widely used carrier is water.
- the compounds of the invention can also be applied in the form of an aerosol composition.
- the active compound is dissolved or dispersed in an inert carrier, which is a pressure-generating propellant mixture.
- the aerosol composition is packaged in a container from which the mixture is dispensed through an atomizing valve.
- Propellant mixtures comprise either low- boiling halocarbons, which may be mixed with organic solvents, or aqueous suspensions pressurized with inert gases or gaseous hydrocarbons.
- the actual amount of compound to be applied to loci of insects, mites, and aphids is not critical and can readily be determined by those skilled in the art in view of the examples above. In general, concentrations of from 10 ppm to 5000 ppm by weight of compound are expected to provide good control. With many of the compoxinds, concentrations of from 100 to 1500 ppm will suffice.
- a suitable application rate for the compounds is about 0.5 to 1.5 lb/Acre, typically applied in 5-20 gal/A of spray formulation containing 1200 to 3600 ppm of compound.
- a suitable application rate is from about 100 to 1500 gal/A spray formulation, which is a rate of 100 to 1000 ppm.
- the locus to which a compound is applied can be any locus inhabited by an insect or arachnid, for example, vegetable crops, fruit and nut trees, grapevines, and ornamental plants.
- an insect or arachnid for example, vegetable crops, fruit and nut trees, grapevines, and ornamental plants.
- mite species are specific to a particular host, the foregoing list of mite species provides exemplification of the. wide range of settings in which the present compounds can be used.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Agronomy & Crop Science (AREA)
- General Health & Medical Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Plural Heterocyclic Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Pretreatment Of Seeds And Plants (AREA)
- Catching Or Destruction (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US21330800P | 2000-06-22 | 2000-06-22 | |
US213308P | 2000-06-22 | ||
PCT/US2001/020135 WO2001098296A2 (en) | 2000-06-22 | 2001-06-22 | 2-(3,5-disubstituted-4-pyridyl)-4-(thienyl, thiazolyl or arylphenyl)-1,3-oxazoline compounds |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1292593A2 true EP1292593A2 (de) | 2003-03-19 |
EP1292593B1 EP1292593B1 (de) | 2006-06-07 |
Family
ID=22794571
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP01950425A Expired - Lifetime EP1292593B1 (de) | 2000-06-22 | 2001-06-22 | 2-(3,5-disubstituierte-4-pyridyl)-4-(thienyl, thiazolyl oder arylphenyl)-1,3-oxazolinverbindungen |
Country Status (14)
Country | Link |
---|---|
US (1) | US6924298B2 (de) |
EP (1) | EP1292593B1 (de) |
JP (2) | JP4963770B2 (de) |
KR (1) | KR100817422B1 (de) |
CN (1) | CN1197862C (de) |
AR (1) | AR029686A1 (de) |
AU (1) | AU2001271418A1 (de) |
BR (1) | BR0112394A (de) |
DE (1) | DE60120402T2 (de) |
EG (1) | EG22745A (de) |
ES (1) | ES2260247T3 (de) |
MX (1) | MXPA03000186A (de) |
TW (1) | TWI275589B (de) |
WO (1) | WO2001098296A2 (de) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6573286B1 (en) | 2002-06-21 | 2003-06-03 | Dow Agrosciences Llc | 2-(2,6-disubstituted phenyl)-4-aryl-5-alkyl-1,3-oxazoline compounds |
US7858666B2 (en) | 2007-06-08 | 2010-12-28 | Mannkind Corporation | IRE-1α inhibitors |
US20130317069A1 (en) * | 2012-05-08 | 2013-11-28 | Dow Agrosciences Llc | 2,4-(substituted aromatic)-1,3-oxazoline compounds as a seed treatment to control pests |
CN103113318A (zh) * | 2013-02-26 | 2013-05-22 | 南京工业大学 | 乙螨唑类新化合物、制备方法及其杀螨活性 |
KR20160067841A (ko) | 2013-08-28 | 2016-06-14 | 메디베이션 테크놀로지즈, 인크. | 헤테로사이클릭 화합물 및 사용 방법 |
JPWO2015060368A1 (ja) | 2013-10-23 | 2017-03-09 | 武田薬品工業株式会社 | 複素環化合物 |
CA2977539A1 (en) | 2015-03-04 | 2016-09-09 | Medivation Technologies, Inc. | Sterol regulatory element-binding proteins (srebps) inhibitors |
EP3265088A1 (de) | 2015-03-04 | 2018-01-10 | Medivation Technologies LLC | Srebp-blocker zur verwendung bei der behandlung von leberfibrose, erhöhtem cholesterin und insulinresistenz |
Family Cites Families (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4977171A (en) | 1988-06-09 | 1990-12-11 | Yashima Chemical Industrial Co., Ltd. | Oxa- or thia-zoline derivative |
AU634608B2 (en) | 1989-12-09 | 1993-02-25 | Kyoyu Agri Co., Ltd. | 2-substituted phenyl-2-oxazoline or thiazoline derivatives, process for producing the same and insectides and acaricides containing the same |
JPH0762006B2 (ja) * | 1989-12-09 | 1995-07-05 | 八州化学工業株式会社 | 2―置換フエニル―2―オキサ―又はチアゾリン誘導体、その製造法及びそれを含有する殺虫・殺ダニ剤 |
JP2888946B2 (ja) | 1990-07-27 | 1999-05-10 | 八洲化学工業株式会社 | オキサゾリン誘導体及びそれを含有する殺虫・殺ダニ剤 |
AU658955B2 (en) | 1992-01-28 | 1995-05-04 | Sumitomo Chemical Company, Limited | An oxazoline derivative, its production and its use |
AU4252893A (en) | 1992-05-26 | 1993-12-30 | E.I. Du Pont De Nemours And Company | Arthropodicidal oxazolines and thiazolines |
JP3443134B2 (ja) * | 1992-05-29 | 2003-09-02 | クミアイ化学工業株式会社 | トリアゾール誘導体及び殺虫、殺ダニ剤 |
JP3209576B2 (ja) * | 1992-06-12 | 2001-09-17 | 八洲化学工業株式会社 | ダニ防除剤 |
JPH06145169A (ja) * | 1992-09-17 | 1994-05-24 | Nippon Soda Co Ltd | 新規な含窒素5員環化合物、その製造方法及び有害生物防除剤 |
TW259693B (de) * | 1993-08-04 | 1995-10-11 | Du Pont | |
JP3279818B2 (ja) * | 1994-06-09 | 2002-04-30 | 八洲化学工業株式会社 | 殺虫・殺ダニ剤 |
TW440429B (en) * | 1994-08-12 | 2001-06-16 | Bayer Ag | Substituted biphenyloxazolines |
EP0784617B1 (de) * | 1994-10-06 | 2002-07-10 | Bayer Ag | Substituierte biphenyloxazoline |
EP0804423A1 (de) * | 1995-01-20 | 1997-11-05 | E.I. Du Pont De Nemours And Company | Oxazoline- und thiazol- derivate alsinsektizide und acarizide |
DE19717228A1 (de) | 1997-04-24 | 1998-10-29 | Bayer Ag | Substituierte Oxazolin-Derivate |
DE19727889A1 (de) | 1997-07-01 | 1999-01-07 | Bayer Ag | 2-(2-Methylphenyl)-oxazoline |
CO5031296A1 (es) | 1997-11-04 | 2001-04-27 | Novartis Ag | Derivados de azolina, compuestos que la contienen y metodo para la preparacion y aplicacion de dicho compuesto |
DE19826671A1 (de) * | 1998-06-16 | 1999-12-23 | Hoechst Schering Agrevo Gmbh | 1,3-Oxazolin- und 1,3-Thiazolin-Derivate, Verfahren zu ihrer Herstellung und ihre Verwendung als Schädlingsbekämpfungsmittel |
WO2000024735A1 (en) * | 1998-10-23 | 2000-05-04 | Dow Agrosciences Llc | Insecticidal 1-(substituted pyridyl)-1,2,4-triazoles |
-
2001
- 2001-06-21 AR ARP010102970A patent/AR029686A1/es unknown
- 2001-06-21 TW TW090115116A patent/TWI275589B/zh not_active IP Right Cessation
- 2001-06-22 WO PCT/US2001/020135 patent/WO2001098296A2/en active IP Right Grant
- 2001-06-22 CN CNB018114504A patent/CN1197862C/zh not_active Expired - Fee Related
- 2001-06-22 EP EP01950425A patent/EP1292593B1/de not_active Expired - Lifetime
- 2001-06-22 US US10/297,418 patent/US6924298B2/en not_active Expired - Fee Related
- 2001-06-22 MX MXPA03000186A patent/MXPA03000186A/es active IP Right Grant
- 2001-06-22 KR KR1020027017435A patent/KR100817422B1/ko not_active IP Right Cessation
- 2001-06-22 AU AU2001271418A patent/AU2001271418A1/en not_active Abandoned
- 2001-06-22 DE DE60120402T patent/DE60120402T2/de not_active Expired - Lifetime
- 2001-06-22 JP JP2002504252A patent/JP4963770B2/ja not_active Expired - Fee Related
- 2001-06-22 BR BR0112394-7A patent/BR0112394A/pt not_active Application Discontinuation
- 2001-06-22 ES ES01950425T patent/ES2260247T3/es not_active Expired - Lifetime
- 2001-06-23 EG EG20010677A patent/EG22745A/xx active
-
2012
- 2012-02-08 JP JP2012024831A patent/JP5437411B2/ja not_active Expired - Fee Related
Non-Patent Citations (1)
Title |
---|
See references of WO0198296A2 * |
Also Published As
Publication number | Publication date |
---|---|
AR029686A1 (es) | 2003-07-10 |
JP4963770B2 (ja) | 2012-06-27 |
DE60120402D1 (de) | 2006-07-20 |
MXPA03000186A (es) | 2003-10-15 |
WO2001098296A2 (en) | 2001-12-27 |
WO2001098296A3 (en) | 2002-06-06 |
EG22745A (en) | 2003-07-30 |
KR20030014274A (ko) | 2003-02-15 |
JP2004501149A (ja) | 2004-01-15 |
EP1292593B1 (de) | 2006-06-07 |
CN1197862C (zh) | 2005-04-20 |
CN1439007A (zh) | 2003-08-27 |
TWI275589B (en) | 2007-03-11 |
BR0112394A (pt) | 2003-07-08 |
AU2001271418A1 (en) | 2002-01-02 |
DE60120402T2 (de) | 2006-10-19 |
ES2260247T3 (es) | 2006-11-01 |
JP5437411B2 (ja) | 2014-03-12 |
KR100817422B1 (ko) | 2008-03-27 |
US20040006108A1 (en) | 2004-01-08 |
US6924298B2 (en) | 2005-08-02 |
JP2012136524A (ja) | 2012-07-19 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0922043B1 (de) | Pestizide 3-(substituiertes phenyl)-5-(thienyl oder furyl)-1,2,4-triazole | |
US6413992B1 (en) | 3-(substituted pyridyl)-1,2,4-triazole compounds | |
JP5437411B2 (ja) | 2−(3,5−二置換−4−ピリジル)−4−(チエニル、チアゾリルまたはアリールフェニル)−1,3−オキサゾリン化合物 | |
US20090215623A1 (en) | Insecticidal 3-acylaminobenzanilides | |
WO2009131237A1 (ja) | 有害節足動物防除組成物および縮合複素環化合物 | |
CZ394097A3 (cs) | Artropodicidní a fungicidní amidy | |
US6417187B2 (en) | 1,2,4-triazole based compounds that can be used as insecticides or acaricides and processes | |
US6413997B1 (en) | 3-(substituted phenyl)-5-(substituted heterocyclyl)-1,2,4-triazole compounds | |
JP2004508309A (ja) | 除草活性を持った5−ベンジルオキシメチル−1,2−イソオキサゾリン誘導体 | |
WO2001034568A1 (fr) | Composes oxime o-ether et fongicides utiles dans l'agriculture et l'horticulture | |
JP2000503013A (ja) | オキサゾリン殺節足動物剤 | |
WO1996001257A1 (fr) | Nouveau compose du type triazol, son procede de production, et agent pesticide | |
EP1123281B1 (de) | 3-(substituiertes phenyl)-5-(substituiertes cyclopropyl)-1,2,4-triazolverbindungen | |
AU2002335751A1 (en) | Insecticidal 3-(2,6-disubstituted phenyl)-5-[4- or 5-arylthien-2- or -3-yl]-1,2,4-triazoles | |
EP1425278A1 (de) | INSEKTIZIDE 3 (2,6 DISUBSTITUIERTES PHENYL) 5 ç4 ODER 5 ARYLTHIEN 2 ODER 3 YL! 1,2,4 TRIAZOLE | |
JP2762505B2 (ja) | 縮合ヘテロ環誘導体、その製法及び除草剤 | |
JPH08217754A (ja) | イミダゾール化合物、殺虫・殺ダニ剤及び農園芸用殺菌剤 | |
EP1397353A1 (de) | 2-(2,6-disubstituierte phenyl)-4-aryl-5-alkyl-1,3-oxazoline derivate zur verwendung als insektizide und acarizide | |
AU2002345791A1 (en) | 2-(2,6-disubstituted phenyl)-4-aryl-5-alkyl-1,3-oxazoline compounds useful as insecticides and acaricides | |
JPH10513156A (ja) | 殺節足動物性オキサジン類およびチアジン類 | |
KR20010040880A (ko) | 살충성 디히드로-옥사디아진, -티아디아진 및 -트리아진 | |
JPH0649699B2 (ja) | ニトロメチレン誘導体、その製法及び殺虫剤 | |
JPH06122681A (ja) | 置換ニトログアニジン誘導体、その製造方法、該誘導体を有効成分として含有する殺虫剤および中間体、その製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20021212 |
|
AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR |
|
AX | Request for extension of the european patent |
Extension state: AL LT LV MK RO SI |
|
RBV | Designated contracting states (corrected) |
Designated state(s): AT BE CH CY DE ES FR GB IT LI |
|
17Q | First examination report despatched |
Effective date: 20040818 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
RBV | Designated contracting states (corrected) |
Designated state(s): DE ES FR GB IT |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): DE ES FR GB IT |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REF | Corresponds to: |
Ref document number: 60120402 Country of ref document: DE Date of ref document: 20060720 Kind code of ref document: P |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2260247 Country of ref document: ES Kind code of ref document: T3 |
|
ET | Fr: translation filed | ||
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed |
Effective date: 20070308 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 15 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20150512 Year of fee payment: 15 Ref country code: DE Payment date: 20150616 Year of fee payment: 15 Ref country code: GB Payment date: 20150617 Year of fee payment: 15 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20150608 Year of fee payment: 15 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20150625 Year of fee payment: 15 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 60120402 Country of ref document: DE |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20160622 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20170228 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20160630 Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20170103 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20160622 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20160622 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20160623 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20181129 |